2-Propenoic acid, 2-cyano-3-ethoxy-, ethyl ester → ethyl 5-amino-1-(tert-butyl)-1H-pyrazole-4-carboxylate
Reaction equation
Cl.[C:2]([NH:6][NH2:7])([CH3:5])([CH3:4])[CH3:3].C([O-])(=O)C.[Na+].C(O[CH:16]=[C:17]([C:23]#[N:24])[C:18]([O:20][CH2:21][CH3:22])=[O:19])C>C(O)C>[NH2:24][C:23]1[N:6]([C:2]([CH3:5])([CH3:4])[CH3:3])[N:7]=[CH:16][C:17]=1[C:18]([O:20][CH2:21][CH3:22])=[O:19]Participants
5
Procedure
A solution of tert-butylhydrazine monohydrochloride (13.9 g, 111.55 mmol), sodium acetate (11.44 g, 139.43 mmol) and ethyl 2-(ethoxymethylene)-2-cyanoacetate (19 g, 112.31 mmol) in ethanol (130 mL) was heated under reflux for 20 hr. Ethanol was evaporated under reduced pressure, and ethyl acetate was added to the residue. The solution was washed with aqueous sodium hydrogen carbonate solution and saturated brine and dried, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (solvent gradient; 2→35% ethyl acetate/hexane) to give ethyl 5-amino-1-tert-butyl-1H-pyrazole-4-carboxylate (24 g, 111.55 mmol, 102%) as a pale-yellow oil.
Workup
- temperatureunder reflux for 20 hr
- customEthanol was evaporated under reduced pressure, and ethyl acetate
- additionwas added to the residue
- washThe solution was washed with aqueous sodium hydrogen carbonate solution and saturated brine
- customdried
- customthe solvent was evaporated under reduced pressure
- customThe residue was purified by silica gel column chromatography (solvent gradient; 2→35% ethyl acetate/hexane)
Sources & evidence
- ORD record
- ord-4a635408892649c4b06ba64860294717
- Source dataset
- uspto-grants-2015_10
- Patent number
- US09156837B2
Reaction notes
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